Synthetic resin from dihaloalkyl xylene and polyalkylene polyamines



Patented Nov. 10, 19 59 ammonia. A typical formula for the amines employed in the reaction may be represented as follows:

SYNTHETIC RESIN FROM DIHALOALKYD Harri E1 XYLENE AND POLYALKYLENE POLY- L AMINES 5 where the group R is an alkylene group and n is a whole John J. Jaruzelski, Pittsburgh, Pa., assignor to Pittsburgh number from 1 W611 highef- R y b6 meth- Plate Glass Company, Allegheny County, Pa., a corylene, ethylene, propylene, butylene, alpha,alphaxylylene, poration of Pennsylvania or the like. Those containing 2 to 4 carbon atoms are representative. No fi gg gggggg 1956 10 The halomethyl derivatives of alkylated benzenes which may be reacted with the foregoing long chain 2 Claims. (Cl. 260-21) amines may be'represented by the structural formula: This invention relates to polyamine resins and it has Y E 1ogen] particular relation to polyamine resins which have valu- 1 able acid absorbing properties, where Ar s a benzene rmg; n is a Whole number from It has heretofore been recognized that highly versatile 1 to "2 1S a Whole P 2 t0 3; y y be halomethyl derivatives of alkylated benzenes, such as methyl y halogen 1S chlorine, blfflmlne lodll'lexylene, could be prepared by reacting said alkylated sPeclfic fixamples of compounds of thls Class compllse benzenes with formaldehyde in the presence of a hydrodlchlommethyl'xylenes of the formula: gen halide, such as hydrochloric acid. Appropriate techniques of preparing such compounds are disclosed in CH 01 an application of Alfred R. Bader, Serial Number CHRCI 463,801, filed October 21, 1954, and again in an application of Frank Fekete, Serial Number 557,451, filed uary 1956, Patent or dichloromethyl mesitylene of the formula:

It has heretofore been suggested to absorb acids from liquid media by means of certain resins and notably certain anion exchange resins in free base form. In 8g "-CH=C1 most instances, the resins are of porous character and are 2: :CH2C1 also employed in a particulate form such as beads or granules. Obviously, the resins should be insoluble and chemically resistant in the medium. They should also The reaction of the long chain amine compounds and be adapted to be regenerated by treatment with an apthe halomethyl substituted alkylated benzene may be propriate alkali. represented by the followingequation:

CH halogen H Heat MeOH H;NR-N-R-NH: (Alkyl),. -Ar

L .i A aqueous CH; halogen Y N- R- R-l% CH An-OHz- -R R CH -Ar-CHQ halogen MeCl H 0 lkyl) 11 This invention is based upon the discovery that halomethyl derivatives and notably dihalomethyl derivatives of alkylated benzenes, such as Xylene, can readily be reacted with amines and preferably amines containing a substantial series of amino groups interconnected by alkyl chains to form resinous polyamines which apparently are long chain compounds comprising the hydrocarbon" portions of the halomethyl alkylated benzenes interconnected by chains comprising alternate alkylene hydrocarbon groups and amino groups. The invention further involves the discovery that the polyamines are porous, insoluble materials having valuable acid absorbing properties and can be regenerated by treatment with base to permit a repetition of the cycle. They are, therefore, adapted for use as acid absorbing media.

In the reaction to form the resins of this invention, various amines of long chain structure may be employed. Usually the chains should contain both primary and secondary amine groups and there should be at least three amino groups in the chain. Such compounds may be -prepared, for example, by the reaction of an unsaturated compound, such as ethylene dichloride with The groups Y may be hydrogen or polymer groups similar to the parenthetical lkyl) n in and 11 have the significance previously given and n is a whole number of a value ofat least 1 and increases with the length of the chain. The latter is of suflicient length that the product is insoluble, eg. 20 or less.

The preparation of halomethyl .alk'ylatedbenzenes-for use in the preparation of the ion exchange resins of this invention may be conducted .co-nveniently biy the interaction of an .alkylated benzene, such as ix-ylene, with formaldehyde in the presence of a hydrohalide, such as One or more of the groups Y may hydrogen chloride. The techniques of such preparation are illustrated by the following example:

Example I Tetraethylene pentamine 63 grams (0.33 mole).

Dichloromethyl-xylene 110 grams (0.55 mole). Methanol 200 milliliters. Celite 25 grams.

The benzene constitutes an inert reaction medium. The Celite provides a filler or carrier for the resin material. The foregoing mixture is refluxed for 5% hours and an additional 20 grams (0.10 mole) of dichloromethyl-xylene are added. Heating is continued for 1 /2 hours and the mixture is poured into an excess of 7 percent aqueous sodium hydroxide solution. The mixture is heated for approximately 2 hours longer and the solid is filtered ofl, washed several times, ground and dried for 3 hours at 95 C. The product is obtained in a yield of 274 grams and contains approximately 38 percent of moisture and is of a density of 0.37 gram per milliliter. The product is then soaked and washed with distilled water and dried at room temperature for 24 hours to a moisture content of 59 percent. The dried material amounted to 417 grams. The granular product is of the following analysis:

Percent Nitrogen 4.87 Silica (SiO 5.37

This resinous product has anion absorbing properties as is demonstrated by the following tests.

The resin is soaked in an excess of 0.3 normal hydrochloric acid and is filtered from the acid solution. Upon washing the resin with distilled water and titrating the filtrate with sodium hydroxide, it is found that acid is taken up by the resin. The acid absorption capacity of the material as initially obtained with 38 percent of moisture is 1.85 milliequivalents per gram.

The sample of material containing 49 percent of moisture was found to pick up 1.27 milliequivalents of acid per gram. This resin body could be employed as anion exchange resin to remove anions from aqueous solutions.

The resin may be regenerated by treating it with an aqueous alkali, such as sodium hydroxide, in order to remove anions.

Example 11 Mesitylene grams 120 Formaldehyde (37 percent aqueous solution) milliliters-.. 300 Hydrochloric acid (concentrated) do 300 Zinc chloride (catalyst) grams The foregoing components are charged into a threenecked glass flask which is provided with the appropriate appurtenances, namely a reflux condenser, a thermometer and an inlet for hydrogen chloride gas. The charge is heated to 90 C. while anhydrous hydrogen chloride is introduced. The reaction is continued for 6 hours after which, the reaction mixture is cooled. The solid products are filtered off, washed with water and recrystallized from 41 heptane. The product is a white crystalline material of the structure:

ClCHz- CHzCl (M.P. 101 to 103 C.)

Example III In accordance with this example, substitute dichloro methyl-mesitylene for the dichloromethyl-xylene in Example I and proceed as in the former example.

The resins of this invention may be alkylated, as for example by treating the resin product of Example I with an alkyl halide, such as methyl iodide. The resultant quaternary salt may be used as an anion exchange resin, or it may be converted into a base by treatment with caustic, such as sodium or potassium hydroxide. The resin may be used to take up strong acids in media, such as water.

The following example illustrates the preparation of one such modified resin:

Example IV The starting resin of this example corresponds to that of Example I. A 100 gram sample of this material is reacted with 180 milliliters of 40 percent aqueous formaldehyde containing 1 percent of sodium hydroxide. The mixture is heated until no more moisture evaporates. An gram quantity of methyl iodide dissolved in milliliters of toluene is then added and the mixture is refluxed for 6 hours. The solid resin is filtered ofi and is heated for 3 hours in a 30 percent solution of sodium hydroxide. Water is added and the resin is Washed 3 times, after which it is dried for 24 hours. The product Weighs 65 grams and has a density of 0.51 gram per milliliter.

The resin will absorb 1.49 milliequivalents of I-ICl per milliliter volume.

The forms of the invention as herein given are to be considered as being by way of example. It will be apparent to those skilled in the art that numerous modifications may be made therein without departure from the spirit of the invention or the scope of the appended claims.

I claim:

1. An ion exchange resin which is the product of reaction of tetraethylene pentamine and dichloromethyl xylene, the tetraethylene pentamine being present in a ratio of about 0.65 mole per 0.33 mole of the dichloromethyl xylene, the reaction being between the amine groups of the tetraethylene pentamine and the chlorine groups of the dichloromethyl xylene.

2. An ion exchange resin which is the product of reaction of (A) a long chain polyamine of the structure L J. in which R is of a class consisting of methylene, ethylene, propylene, butylene and n is a number from 1 to 10, and (B) a dihalomethyl xylene, the reaction being be tween the amino groups of the compound (A) and the halogen groups of the compound (B).

References Cited in the file of this patent UNITED STATES PATENTS 2,411,142 Kelso Nov. 19, 1946 2,469,693 Lundberg May 10, 1949 2,546,938 Bauman et al. May 27, 1951 2,588,784 Whittaker et al. Mar. 11, 1952 2,732,352 Blaricom et a1 Jan. 24, 1956 FOREIGN PATENTS 517,738 Great Britain Feb. 7, 1940 652,830 Great Britain May 2, 1951 

1. AN ION EXCHANGE RESIN WHICH IS THE PRODUCT OF REACTION OF TETRAETHYLENE PENTAMINE AND DICHLOROMETHYL XYLENE, THE TETRAETHYLENE PENTAMINE BEING PRESENT IN A RATIO OF ABOUT 0.65 MOLE PER 0.33 MOLE OF THE DICHLOROMETHYL XYLENE, THE REACTION BEING BETWEEN THE AMINE GROUP FO THE TETRAETHYLENE PENTAMINE AND THE CHLORINE GROUPS OF THE DICHLOROMETHYL XYLENE. 